Cleanser for pesticide application means

ABSTRACT

The present invention provides a composition which, when dissolved in an aqueous solution, is capable of removing the organic residue from agricultural pesticides from storage tanks and dispersal systems. The composition of the present invention comprises a combination of (1) from about 72 to about 95 parts by weight of an alkali metal polyphosphate, (2) from about 5 to about 15 parts by weight of an organic detergent, (3) from about 0.02 to about 0.5 parts by weight of an alkali metal chromate and from about 0.2 to about 5 parts by weight of an alkali metal meta-silicate or an alkali metal sesqui-silicate or an alkali metal ortho-silicate, (4) from about 0.5 to about 8 parts by weight of a chelating agent, and, preferably, (5) a watersoluble, high dilution tracer dye in amounts of from about 0.01 to about 0.5 parts by weight.

United States Patent [191 Mommer Oct. 21, 1975 1 CLEANSER FOR PESTICIDE APPLICATION MEANS [75] Inventor: Richard Paul Mommer, Loveland,

21 Appl. No; 411,359

[52] US. Cl 134/22 R; 134/26; 252/135; 252/527; 252/539; 252/D1G. 14

[51) Int C1. B0813 15/00; C1 1D 3/065;Cl1D 3/33 [58] Field of Search 252/135, 527, 539, 540, 252/139, DIG. ll, DIG. 14; 134/22 R; 137/15 OTHER PUBLICATIONS The Chemical Formulary, Vol. X111, edited by H. Bennett, Chemical Publishing Co, New York 1967, pp. 382383 Primary ExaminerRalph S. Kendall Assistant Examiner-Dennis Li Albrecht Attorney, Agent, or Fi'rm Lilling & Siegel [57} ABSTRACT The present invention provides a composition which, when dissolved in an aqueous solution, is capable of removing the organic residue from agricultural pesticides from storage tanks and dispersal systems. The composition of the present invention comprises a combination of 1) from about 72 to about 95 parts by weight of an alkali metal polyphosphate, (2) from about 5 to about 15 parts by weight of an organic detergent, (3) from about O02 to about 05 parts by weight of an alkali metal chromate and from about 0.2 to about 5 parts by weight of an alkali metal metasilicate or an alkali metal sesqui-silicate or an alkali metal orthosilicate, (4) from about 045 to about 8 parts by weight of a chelating agent, and, preferably, (5) a water-soluble, high dilution tracer dye in amounts of from about 0.01 to about 0.5 parts by weight.

9 Claims, N0 Drawings CLEANSER FOR PESTICIDE APPLICATION MEANS Modern farming requires the use of potent chemical agents. all of which must be handled and disposed of with extreme care. None perhaps are more potent, and thus more dangerous to the farmer or his employees, and as well to the general public, than the various pesticide compositions, including herbicides and insecticides, used by the farmer to protect his growing crops. Although the dangers of using these chemicals is wellknown, the rapid population growth of the planet, requires their use in order to maintain the necessary output of food.

Generally, these pesticides are applied to the farmers land or to the growing crops by various spray means, generally comprising a storage tank in which the pesticide is kept and a piping system through which the pesticide is carried to be finally expelled through a nozzle. The storage tank can range from a portable, hand-carried tank, operated by a pump or compressed gas charge, to a relatively massive, permanently installed, ground installation, measured in the thousands of gallons, from which the pesticide is dispersed through extensive piping arrangements to the fields. Such tanks include, therefore, one gallon hand-spray tanks, 15, 30, 55 or 500 gallon wheel-mounted tanks, which are portable but can be moved only with the use of tractors or other engine-driven vehicles. The tanks can be formed, for example, of steel, aluminum, or even fiberglass with steel being, at least up to the present, the material of choice for both the tanks and the conduit pipe.

The modern farmer, generally not utilizing his fields for only a single crop, therefore faces a wide range of problems which have been controlled by chemical pesticides. This wide variety of crops that are now growing in a single modern farm also require a correspondingly wide variety of pesticides.

The majority of pesticides used today are formed primarily of organic chemicals which in many cases are not water-soluble. A problem which has been encountered, and to date not completely successfully met, is the cleaning of the tank and dispersal system so as to remove substantially all of the residue from the pesticide after it has been used and before adding another pesticide. In many cases, the different pesticides, even in relatively minute quantities, can be mutually antagonistic or can be harmful to another crop. [t is for this reason that residues, even in the part per million (ppm) range, are considered undesirable and even can prevent the continued use of a tank or spray system for another, different pesticide. Because of the generally large sizes of the tank and dispersal equipment, it would not be economically feasible to utilize nonaqueous cleaner for this purpose. Accordingly, the farmer has attempted to use plain water to flush his tanks to remove the residue ofa previously utilized pesticide before adding a second pesticide and has also used, for example, water containing, for example, one and a half per cent ammonia and other generally basic aqueous solutions, including, for example, calcium carbonate, an organic detergent and potassium chromate, in one case, and in another case, sodium carbonate, an organic detergent and potassium chromate.

The general metal-cleaning art, for example, the cleaning of aluminum surfaces prior to anodizing the aluminum, also requires the removal of substantially all oily materials from the surface. Carroll et al, in US. Pat. Re. No. 26,609, describes an aluminum cleaning composition containing a mixture of( l an alkali metal polyphosphate and an alkali metal tetraborate in specific proportions, so as to provide a solution having a pH in the range of from 8 to 10; (2) hexavalent chromium salt, e.g., a chromate; (3) an organic detergent, for example, naphthalene sodium sulfonate; and (4) an aluminum sequestrant, such as polyhydroxy acids, or their alkali metal salts, or salts of EDTA. Carroll further specifies that the use of the sodium polyphosphate and sodium tetraborate, in combination, is necessary in order to obtain the desired cleansing action. Carroll et al further state that although sodium metasilicates have previously been used in aluminum cleaners, it was not recommended for use in their particular composition which was intended specifically for preparing the aluminum surface for subsequent anodization.

Well-site equipment, which is often exposed to hard water, has been treated with mixtures of an alkali metal polyphosphate, a sodium salt of a dihydroxyethyl glycine and a dye; the dye is used solely to give a recognizable color to the water solution and the glycine is added as a stabilizer for the tripolyphosphate.

Unfortunately, the art has not to date been able to provide the farmer with a highly efficient and safe cleansing agent which is capable of removing the residue of at least the most common organic pesticides and maintaining the tank and dispersal system in a clean, operative condition.

This invention provides such a material which is water-soluble, and when dissolved in water, in an amount from about 0.2 to about 5 pounds per l00 gallons of water, is capable of substantially decreasing the amounts of organic residue in a dispersal system compared to the other available cleansing products.

In accordance with the present invention, there is provided a composition which, when dissolved in an aqueous solution, is capable of removing the organic residue from agricultural pesticides from storage tanks and dispersal systems.

The composition of the present invention comprises a combination of 1) from about 72 to about parts by weight of an alkali metal polyphosphate, (2) from about 5 to about 15 parts by weight of an organic detergent, (3) from about 0.02 to about 0.5 parts by weight of an alkali metal chromate and from about 0.2 to about 5 parts by weight of an alkali metal meta-silicate or an alkali metal sesqui-silicate or an alkali metal ortho-silicate, (4) from about 0.5 to about 8 parts by weight of an alkali metal salt of a dihydroxyethyl glycine, and, preferably, (5) a water-soluble, high-dilution tracer dye in amounts of from about 0.0l to about 0.5 parts by weight. This invention further provides an aqueous solution containing the above composition and a process for cleansing agricultural spraying equipment to remove the organic residues of agricultural pesticides therefrom, the process comprising contacting the tank surfaces with an aqueous solution of the above-identified composition, followed by flushing the tank surfaces with pure water until the flush water runs colorless indicating substantial removal of all of the cleansing solution.

Substantially any alkali metal polyphosphate can be utilized in accordance with the present invention. Sodium and potassium polyphosphates, however, are preferred, as these are the most readily available. Any of the polyphosphates are found to be effective in the present composition as providing the necessary alkalinity to the aqueous solution and further acting in a synergistic manner with the detergent which is present. Such polyphosphates include, for example, sodium tripolyphosphate, potassium tripolyphosphate, sodium pyrophosphate, potassium pyrophosphate, sodium hexametaphosphate and potassium hexametaphosphate.

Generally, from 72 to about 95 parts by weight of the polyphosphate salt is present in the composition, however, preferably from about 84 to about 90 per cent by weight of the alkali metal polyphosphate is present.

The alkali metal polyphosphates provide the neces sary neutralizing action for neutralizing any organic acid residue in the tank, and further aid cleansing action in combination with any organic detergent which is present.

An organic detergent, preferably a low sudsing detergent, is present to aid in the removal of any organic residue which may be present when utilizing an aqueous solution of the claimed combination. Usually such organic detergents include specially the alkyl aryl sul phonic acids and their alkali metal or ammonium salts and alkylphenol-ethylene oxide condensation products. The condensed naphthalene sodium sulphonates are also useful, but preferably are used in combination with one or more of the above-identified ingredients.

The alkyl aryl sulphonates are most preferred and among the commercially available examples of these materials the alkyl components have from 8 to 14 carbon atoms and the aryl components are preferably benzene and naphthalene. Examples of such materials are dodecylbenzene sulphonic acid, sodium dodecylbenzene sulphonate, sodium dinaphthyl methane disulphonate, and ammonium dodecylbenzene sulphonate.

The alkylphenol-ethylene oxide condensation products which are most useful, have the formula:

wherein R is an alkyl group having from 4 to 16 carbon atoms and where n has a value of from 6 to 16. Preferred R groups are the octyl and nonyl groups. A commercial example of such a condensate comprises a mixed composition wherein R can be an alkyl group having from 6 to 12 carbon atoms, and where n has a value of from 8 to 12 (Tergitol-NPX).

The above detergent material can be present in amounts of from about to about 15 parts by weight of a total combined composition and preferably from about 8 to about 12 parts by weight.

Commercially available alkylphenol-ethylene oxide condensates includes the lGEPALS. Other useful de tergents include the poly(oxyethylene) derivatives of the fat forming fatty acids of at least about 12 carbon atoms, of alcohols, of phenols, of amides or of amines; Alkyl poly(ethoxy) phenols; poly(oxyethylene) sorbitan monostearate', polyoxyethylene sorbitan monolaurate alkyl aryl polyether sulphates; the polyoxyethylene derivatives of propylene glycol and the lignin sulphonates.

The tracer dye can be substantially any water-soluble dye which can impart a relatively intense color to a water solution in highly dilute concentrations. For ex ample, in the range of from about 0.05 to about l ppm. Preferred such dyes include dyes derived from watersoluble xanthene class dyes. The materials are watersoluble and give off a strong fluorescence in the visible range at extreme dilution. A preferred material is fluorescein, which provides a visible, greenish fluorescence at dilutions in water as high as 1:40,000,000. Other useful tracer dyes of this class include chrysoline, fuchsine and Rhodamine. Such dyes are generally present in amounts of at least about 001 parts by weight of the dry composition and preferably at least about 0,] Generally more than about 0.5 parts by weight is not needed and would be wasted. However, if desired for any other reason, such additional amounts of dye can be present and still fall in the scope of the present invention.

The dry composition of the present invention, comprising the alkali metal polyphosphate, the detergent, the chromate, the silicate, the chelating agent and the dye, can be admixed in the dry state and then admixed with water in the desired proportion to form the cleansing aqueous solution. Alternatively, of course, the individual components can be admixed with water, in whatever order, in order to form the desired aqueous flush solution. It is only necessary that all of the components be present together in order to form the desired cleansing solution having the properties of not only removing substantially all of the organic acid residues left in spray equipment from agricultural pesticides but also providing an indicating means to determine when the storage tank and the spray system has been completely flushed.

Generally, at least about 0.2 pounds of the abovedefined composition per 100 gallons of water is required to form a useful cleansing composition. Preferably from about 0.7 to about 4 pounds per 100 gallons would be most useful. Where the storage and spray system to be cleaned has previously been filled with acidic organic material, including liquid fertilizers and certain organic acid pesticides, generally at least about 1.5 pounds per 100 gallons of water should be used. Generally, in cleaning out such a system, the system is first flushed with pure water to remove the majority of any residue present in the system by physical flushing and to remove any loose solid particles. The system is then filled with the cleansing material and the cleanser is then flushed out through the sprayer from the storage system, ensuring that all portions of the spray system are flushed. Generally the system should next be flushed at least twice with water to ensure the removal of all of the cleansing solution prior to refilling the system with new pesticide.

The following examples are merely intended to provide a description of preferred embodiments of the 7 present invention showing the use of the claimed com- EXAMPLES 1 THROUGH 6 A 5-gallon mixture comprising per cent by weight water and 10 per cent by weight of the amine salt of 2,4-dichlorophenoxyacetic acid (2,4-D-amine) was added to a 5-gallon container, which was then emptied and dried. An aqueous solution was prepared compris ing one pound of the following dry composition per a hundred gallons of water:

Sodium salt of di(heta-hydroxycthyl) glycine (Verscne Fer-3) 2 Fluorescein dye 0.l

Five gallons of the above solution were placed into the dried 5-gallon container, mixed, emptied, and the container was then flushed twice again with pure water. The residue remaining in the tank following the second water flushing was collected and analyzed. The residue in the tank showed substantially no dye color.

The above treatment was repeated with a S-gallon container filled with a 2,4-D-ester compound, with ethyl Parathion, methyl Parathion, endrin (an insecticide) and Banvel-D. In each case the residue in the tank following the second water-flushing was collected and analyzed. The analyses are set forth in the table below.

Table 1 Example No. Pesticide PPM, Residue Analyzed l 2.4D-amine 82 2 2.4- L.V. Ester M00 3 Banvel 4.6 4 Ethyl Parathion 8.8 5 Methyl Parathion 44 6 Endrin 56 Table 2 Pesticide Residue (ppm) Comparative Water Commercial Household Only Cleanser Ammonia 2,4-D-Amine 1080 750 No data 2.4-D L.V. Ester 14000 5100 No data Banvel-D 6.4 8.2 l0.6 Ethyl Parathion 7.5 22 No data Methyl Parathion 50 $0 No data Endrin 70 62 No data As is shown from the above tables, the composition, in accordance with the present invention, causes a substantial reduction in the residue of the organic pesticide present in the tank, following the cleaning, and it is especially effective with the most commonly used 2,4-D- amine.

. A further investigation of the interlor of the tank showed a general reduction in the rust and scale present on the surface of the tank following cleaning with the composition of the present invention compared to the condition of the interior of the tank following cleaning with water, a commercial material or household ammonia.

[n the above tests, the cleansing agent was permitted to remain within the tank, while being mixed, for a total of 10 minutes, each ofthe two subsequent water flushes also lasted 10 minutes.

I claim:

I. A composition for removing the organic residue of agricultural pesticides from storage tanks and dispersal systems, the composition comprising the combination of l from about 72 to about parts by weight of an alkali metal polyphosphate; (2) from about 5 to about l5 parts by weight of an organic detergent; (3) from about 0.02 to about 0.5 part by weight of an alkali metal chromate and from about 0.2 to about 5 parts by weight of a silicate salt selected from the group consisting of alkali metal meta-silicates, alkali metal sesquisilicates and alkali metal ortho-silicates; (4) from about 0.5 to about 8 parts by weight of an alkali metal salt of a dihydroxyethyl glycine; and (5) a watensoluble dye, capable of providing a visible color in basic aqueous solutions at a dilution of as low as 1 ppm, in an amount of at least about 0.01 part by weight.

2. The composition of claim 1, wherein the alkali metal chromate is potassium chromate and wherein the other alkali metal salts are sodium salts.

3. The composition of claim 2, wherein the organic detergent is selected from the group consisting of the sodium salts of the sulfonated condensation products of naphthalene and formaldehyde; alkyl aryl sulfonic acids and their alkali metal salts, in which the alkyl group is C: to C and the aryl group is benzene and naphthalene; and an alkyl phenol-ethylene oxide condensate having the formula:

where R is an alkyl group having from 4 to 16 carbon atoms and where n has a value of from 6 to 16.

4. The composition of claim 2 wherein the dye is a fluorescein dye.

5. The composition of claim 4, wherein the alkali metal polyphosphate is sodium tripolyphosphate.

6. The composition of claim 5, wherein the silicate is sodium meta-silicate.

7. An aqueous solution for flushing out the organic residue of agricultural pesticides from storage tank and dispersal systems, the aqueous solution comprising for each gallons of water from about 0.2 to about four pounds of a composition comprising the combination of(l from about 72 to about 95 parts by weight of an alkali metal polyphosphate', (2) from about 5 to about 15 parts by weight of an organic detergent; (3) from about 0.02 to about 0.5 part by weight of potassium chromate and 0.2 to about 5 parts by weight of sodium meta-silicate; (4) from about 0.5 to about 8 parts by weight of an alkali metal salt of a dihydroxyethyl glycine; and (5) a watersoluble dye capable of providing a visible color in basic aqueous solutions at a dilution of as low as 1 ppm, in an amount of at least about 0.0l part by weight.

8. A method for removing the organic residues of agricultural pesticides from storage tank and dispersal 15 parts by weight of an organic detergent; (3) from about 0.02 to about 0.5 part by weight of an alkali metal chromate and from about 0.2 to about 5 parts by weight of a silicate salt selected from the group consist ing of alkali metal meta-silicates. alkali metal sesquisilicates and alkali metal ortho-silicates; and (4) from about 0.5 to about 8 parts by weight of an alkali metal salt of a dihydroxyethyl glycine. 

1. A COMPOSITION FOR REMOVING THE ORGANIC RESIDUE OF AGRICULTRAL PESTICIDES FROM STORAGE TANKS AND DISPERSAL SYSTEMS, THE COMPOSITION COMPRISING THE COMBINATION OF (1) FROM ABOUT 72 TO ABOUT 95 PARTS BY WEIGHT OF AN ALKALI METAL POLYPHOSPHATE, (2) FROM ABOUT 5 TO ABOUT 15 PARTS BY WEIGHT OF AN ORGANIC DETERGENT, (3) FROM ABOUT 0.02 TO ABOUT 0.5 PART BY WEIGHT OF AN ALKALI METAL CHROMATE AND FROM ABOUT 0.2 TO ABOUT 5 PARTS BY WEIGHT OF A SILICATE SALT SELECTED FROM THE GROUP CONSISTING OF ALKALI METAL META-SILICATES, ALKALI METAL SESQUI-SILICATES AND ALKALI METAL ORTHO-SILICATES, (4) FROM ABOUT 0.5 TO ABOUT 8 PARTS BY WEIGHT OF AN ALKALI METAL SALT OF A DIHYDROXYETHYL GLYCINE, AND (5) A WATER-SOLUBLE DYE, CAPABLE OF PROVIDING A VISIBLE COLOR IN BASIC AQUEOUS SOLUTIONS AT A DILUTION OF AS LOW AS 1 PPM, IN AN AMOUNT OF AT LEAST ABOUT 0.01 PART BY WEIGHT.
 2. The composition of claim 1, wherein the alkali metal chromate is potassium chromate and wherein the other alkali metal salts are sodium salts.
 3. The composition of claim 2, wherein the organic detergent is selected from the group consisting of the sodium saltS of the sulfonated condensation products of naphthalene and formaldehyde; alkyl aryl sulfonic acids and their alkali metal salts, in which the alkyl group is C2 to C14, and the aryl group is benzene and naphthalene; and an alkyl phenol-ethylene oxide condensate having the formula:
 4. The composition of claim 2 wherein the dye is a fluorescein dye.
 5. The composition of claim 4, wherein the alkali metal polyphosphate is sodium tripolyphosphate.
 6. The composition of claim 5, wherein the silicate is sodium meta-silicate.
 7. An aqueous solution for flushing out the organic residue of agricultural pesticides from storage tank and dispersal systems, the aqueous solution comprising for each 100 gallons of water from about 0.2 to about four pounds of a composition comprising the combination of (1) from about 72 to about 95 parts by weight of an alkali metal polyphosphate; (2) from about 5 to about 15 parts by weight of an organic detergent; (3) from about 0.02 to about 0.5 part by weight of potassium chromate and 0.2 to about 5 parts by weight of sodium meta-silicate; (4) from about 0.5 to about 8 parts by weight of an alkali metal salt of a dihydroxyethyl glycine; and (5) a water-soluble dye capable of providing a visible color in basic aqueous solutions at a dilution of as low as 1 ppm, in an amount of at least about 0.01 part by weight.
 8. A method for removing the organic residues of agricultural pesticides from storage tank and dispersal systems, the method comprising flushing the system with the aqueous solution of claim 7 followed by flushing with water until the flush water shows no visible coloration.
 9. A composition for removing the organic residue of agricultural pesticides from storage tanks and dispersal systems, the composition comprising the combination of (1) from about 72 to about 95 parts by weight of an alkali metal polyphosphate; (2) from about 5 to about 15 parts by weight of an organic detergent; (3) from about 0.02 to about 0.5 part by weight of an alkali metal chromate and from about 0.2 to about 5 parts by weight of a silicate salt selected from the group consisting of alkali metal meta-silicates, alkali metal sesquisilicates and alkali metal ortho-silicates; and (4) from about 0.5 to about 8 parts by weight of an alkali metal salt of a dihydroxyethyl glycine. 